JP2008536805A - 5,6-Dialkyl-7-aminoazolopyrimidines, methods for their preparation, their use for controlling phytopathogenic fungi, and agents containing them - Google Patents

Abstract

[式中、置換基は以下のように定義される：
R¹はアルキル、アルコキシメチレンまたはアルコキシエチレンを表わし、ここで、脂肪族基は説明したように置換されていてもよく；
R²はn-プロピルまたはn-ブチルを表わし；
AはNまたはCHを表わし；
R³はメチル、そしてAがCHを表わす場合にはさらに水素を表わす]
の5,6-ジアルキル-7-アミノアゾロピリミジンに関する。さらに、本発明は該化合物を製造するための方法および中間体生成物、後者を含む薬剤、ならびに植物病原性菌類を防除するための化合物の使用に関する。
【選択図】なしThe present invention relates to formula (I):
[Chemical 1]

[Wherein the substituents are defined as follows:
R ¹ represents alkyl, alkoxymethylene or alkoxyethylene, wherein the aliphatic group may be substituted as described;
R ² represents n-propyl or n-butyl;
A represents N or CH;
R ³ represents methyl and, if A represents CH, further hydrogen]
Of 5,6-dialkyl-7-aminoazolopyrimidine. Furthermore, the present invention relates to methods and intermediate products for the production of the compounds, drugs containing the latter, and the use of the compounds for controlling phytopathogenic fungi.
[Selection figure] None

Description

[式中、置換基は以下に定義される通りである：
R¹はC₅-C₉-アルキル、C₄-C₁₁-アルコキシメチレンまたはC₃-C₁₀-アルコキシエチレンであり、ここで脂肪族基は１〜３つの以下の基によって置換されていてもよく：
シアノ、ニトロ、ヒドロキシル、C₃-C₆-シクロアルキル、C₁-C₆-アルキルチオ、C₅-C₁₂-アルキニルおよびNR^aR^b；
R^aおよびR^bは水素またはC₁-C₆-アルキルであり；
R²はn-プロピルまたはn-ブチルであり；
AはNまたはCHであり；
R³はCH₃、そしてAがCHである場合にはさらに水素である]
の5,6-ジアルキル-7-アミノアゾロピリミジンに関する。 The present invention relates to formula I:

[Wherein the substituents are as defined below:
R ¹ is C ₅ -C ₉ -alkyl, C ₄ -C ₁₁ -alkoxymethylene or C ₃ -C ₁₀ -alkoxyethylene, wherein the aliphatic group may be substituted by 1 to 3 of the following groups: Often:
Cyano, nitro, hydroxyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkylthio, C ₅ -C ₁₂ -alkynyl and NR ^a R ^b ;
R ^a and R ^b are hydrogen or C ₁ -C ₆ -alkyl;
R ² is n-propyl or n-butyl;
A is N or CH;
R ³ is CH ₃ , and further hydrogen when A is CH]
Of 5,6-dialkyl-7-aminoazolopyrimidine.

  Furthermore, the present invention relates to methods for producing these compounds, compositions comprising them and their use for controlling phytopathogenic harmful fungi.

In general, 5,6-dialkyl-7-aminotriazolo- and -pyrazolopyrimidines have been proposed in US Pat. The individual bactericidal activity 5,6-dialkyl-7-aminotriazolo- and -pyrazolopyrimidines are known from US Pat.
British Patent No. 1 1486 629 European Patent Application No. 141317

  However, their activity is not satisfactory in many cases. Based on this, it is an object of the present invention to provide compounds with improved activity and / or broad activity spectrum.

  We have found that this object is achieved by the compounds defined at the outset. Furthermore, methods and intermediates for producing them, compositions containing them, and methods for controlling harmful fungi using Compound I have been found.

  The compounds of formula I differ from the compounds in the above publications by the specific embodiment of the substituent at the 5-position of the azolopyrimidine skeleton.

  Compared to known compounds, the compounds of formula I are more active against harmful fungi.

The compounds of the invention can be obtained by different routes. Advantageously, to obtain a compound of the invention, a substituted β-ketoester of formula II is reacted with an aminoazole of formula III to give a 7-hydroxyazolopyrimidine of formula IV. The substituents in formulas II and IV are as defined for formula I, and the group R in formula II is C ₁ -C ₄ -alkyl, where methyl, ethyl or propyl are preferred for practical reasons.

  The compounds of formula IV are new.

  The reaction of the substituted β-ketoester of formula II with the aminoazole of formula III can be carried out in the presence or absence of a solvent. It is advantageous to use solvents in which the starting materials are substantially inert and in which they are completely or partially dissolved. Suitable solvents are in particular alcohols such as ethanol, propanol, butanol, glycol, glycol monoether, diethylene glycol or their monoethers, aromatic hydrocarbons such as toluene, benzene or mesitylene, dimethylformamide, diethylformamide, dibutylformamide. Or an amide such as N, N-dimethylacetamide, a lower alkanoic acid such as formic acid, acetic acid or propionic acid, or an alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal oxide, alkaline earth metal oxide, Alkali metal hydrides, alkaline earth metal hydrides, alkali metal amides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates, organometallic compounds, especially alkali metal alkyls, alkyl magnetoses Um halides, alkali metal alkoxides, alkaline earth metal alkoxides and dimethoxy magnesium, and organic bases (eg tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted Bases such as pyridine (eg collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines) and mixtures of these solvents with water. Suitable catalysts are bases as described above, or acids such as sulfonic acids or inorganic acids. Particularly preferably, this reaction is carried out without solvent or in chlorobenzene, xylene, dimethyl sulfoxide or N-methylpyrrolidone. Particularly preferred bases are tertiary amines such as triisopropylamine, tributylamine, N-methylmorpholine or N-methylpiperidine. If the reaction is carried out in a solvent, the temperature is 50-300 ° C., preferably 50-180 ° C. (see: EP 770615; Adv. Het. Chem. 57 (1993), 81ff].

Usually, the base is used in catalytic amounts. However, it can also be used as an equimolar amount, in excess, or as a solvent where appropriate.

  In many cases, the resulting condensate of formula IV precipitates in pure form from the reaction solution, is washed with the same solvent or water, and subsequently dried, followed by a halogenating agent, in particular a chlorinating agent or bromine. Reaction with an agent yields a compound of formula V where Hal is chlorine or bromine, in particular chlorine. Preferably, this reaction is carried out at 50 ° C. to 150 ° C. using a chlorinating agent such as phosphorus oxychloride, thionyl chloride or sulfuryl chloride, preferably in an excess of trichloride phosphate at the reflux temperature. After evaporating excess trichloride phosphate, the residue is treated with ice water, if appropriate with a solvent that is not miscible with water. In many cases, the chlorination product isolated from the dried organic layer, if appropriate after evaporation of the inert solvent, is very pure and then in an inert solvent at 100 ° C. to 200 ° C. React with ammonia at ° C to give 7-aminoazolo [1,5-a] pyrimidine. Preferably, the reaction is carried out using a 1-10 molar excess of ammonia under a pressure of 1-100 bar.

  The novel 7-aminoazolo [1,5-a] pyrimidine is isolated as a crystalline compound by evaporating the solvent if appropriate and then dissolving in water.

  Β-ketoesters of formula II can be prepared as described in Organic Synthesis Coll. Vol. 1, p. 248 and / or they are commercially available.

  The intermediate of formula V is novel.

Alternatively, novel compounds of formula I can be obtained by reacting a substituted acyl cyanide of formula VI where R ¹ and R ² are as defined above with an aminoazole of formula III. .

  This reaction can be carried out in the presence of a solvent or without a solvent. It is advantageous to use solvents in which the starting materials are substantially inert and in which they are completely or partially dissolved. Suitable solvents are in particular alcohols such as ethanol, propanol, butanol, glycol, glycol monoether, diethylene glycol or their monoethers, aromatic hydrocarbons such as toluene, benzene or mesitylene, dimethylformamide, diethylformamide, dibutylformamide. Or an amide such as N, N-dimethylacetamide, a lower alkanoic acid such as formic acid, acetic acid or propionic acid, or a base as described above, and a mixture of these solvents and water. If the reaction is carried out in a solvent, the reaction temperature is 50 to 300 ° C, preferably 50 to 150 ° C.

  The novel 7-aminoazolo [1,5-a] pyrimidines of formula I are isolated as crystalline compounds, if appropriate after evaporation of the solvent or after dilution with water.

  Some of the substituted alkyl cyanides of formula VI required to prepare 7-aminoazolo [1,5-a] pyrimidines are known and strong bases (eg alkali metal hydrides, alkali metal alkoxides, alkali metals Amide or metal alkyl) can be prepared from alkyl cyanides and carboxylic esters by known methods (see J. Amer. Chem. Soc. 73, (1951), p. 3766).

  If an individual compound I cannot be obtained by the above route, it can be prepared by derivatizing another compound I.

  Even if a mixture of isomers is formed during the synthesis, in some cases, individual isomers may be interconverted during work-up for use or during application (eg during the action of light, acid or base). Usually, separation is not necessarily required. Such conversion can occur after use, for example, during the treatment of plants, in treated plants, or even in harmful fungi to be controlled.

  In defining symbols in the above formulas, the following collective terms are generally used to represent the following substituents:

  Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated straight-chain or mono- or double-branched hydrocarbon groups having 1 to 4 or 5 to 9 carbon atoms, such as C ₁ -C ₆ -alkyl (methyl, ethyl, propyl, 1- Methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, Hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2 -Trimethylpropyl, 1-ethyl-1-methylpropyl and 1- Ethyl-2-methylpropyl);

  Alkoxymethylene and alkoxyethylene: saturated linear or mono-branched, double-branched or triple-branched hydrocarbon chains linked via a methyleneoxy group and an ethyleneoxy group, respectively, eg having 3 to 11 carbon atoms as described above Hydrocarbon chains (eg propoxyethyl, butoxyethyl, pentoxyethyl, hexyloxyethyl, heptyloxyethyl, octyloxyethyl, nonyloxyethyl, 3- (3-ethylhexyloxy) ethyl, 3- (2,4,4 -Trimethylpentyloxy) ethyl, 3- (1-ethyl-3-methylbutoxy) ethyl, ethoxypropyl, propoxypropyl, butoxypropyl, pentoxypropyl, hexyloxypropyl, heptyloxypropyl, octyloxypropyl, nonyloxypropyl, 3- (3-Ethylhexyloxy) propyl (Lopyl, 3- (2,4,4-trimethylpentyloxy) propyl, 3- (1-ethyl-3-methylbutoxy) propyl).

  The scope of the present invention includes (R) and (S) isomers and racemates of compounds of formula I having a chiral center.

  From the standpoint of the intended use of the azolopyrimidine of formula I, the following substituents are particularly preferred in each case alone or in combination.

The alkyl group in R ¹ of formula I is preferably a linear or mono-branched, double-branched or triple-branched alkyl group, and the alkyl group preferably has no substituent.

[式中、R¹¹はC₃-C₁₀-アルキルまたはC₅-C₁₀-アルコキシアルキルであり、R¹²はC₁-C₄-アルキル、特にメチルであり、R¹¹およびR¹²は一緒に最大で１２個の炭素原子を有し、無置換であるか、あるいは式ＩにおけるR¹と同様に置換基されていてもよい]
で記載される。 Furthermore, compounds of formula I which are branched at the α-carbon atom in R ¹ are preferred. They are of formula Ia:

[Wherein R ¹¹ is C ₃ -C ₁₀ -alkyl or C ₅ -C ₁₀ -alkoxyalkyl, R ¹² is C ₁ -C ₄ -alkyl, especially methyl, and R ¹¹ and R ¹² together It has a maximum of 12 carbon atoms and is unsubstituted or optionally substituted like R ¹ in formula I]
It is described in.

If R ¹ is an alkyl group substituted by cyano, the cyano group is preferably on the terminal carbon atom.

In one embodiment of Compound I of the invention, R ¹ is C ₅ -C ₉ -alkyl, C ₄ -C ₁₁ -alkoxymethylene or C ₃ -C ₁₀ -alkoxyethylene. For these groups, C ₄ -C ₁₀ -alkoxy chains are preferred.

R ¹ is hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2- Dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methyl Particularly preferred is Compound I which is propyl or 1-ethyl-2-methylpropyl.

Further preferred are compounds of formula I, wherein R ¹ is n-heptyl, 1-methylhexyl, n-octyl, 1-methylheptyl, n-nonyl, 1-methyloctyl and 3,5,5-trimethylhexyl. .

In one embodiment of Compound I of the present invention, R ² is n-propyl.

In another embodiment of Compound I of the present invention, R ² is n-butyl.

In a preferred embodiment of the compounds of the present invention, R ³ is methyl.

に相当する。 One embodiment relates to compound I, wherein A is CH. These compounds have the formula I. 1:

It corresponds to.

に相当する。 Another embodiment of the compounds of the invention relates to compound I, wherein A is N. These compounds have the formula I. 2:

It corresponds to.

  For their use, the compounds I listed in the table below are particularly preferred. Furthermore, the groups described for the substituents in the table are themselves particularly preferred embodiments of the substituents in question, independent of the combination in which they are described.

Table 1
For each compound, R ¹ corresponds to one row of Table A, R ² is n-propyl, and R ³ is hydrogen. 1 compound.

Table 2
For each compound, R ¹ corresponds to one row of Table A, R ² is n-butyl, and R ³ is hydrogen. 1 compound.

Table 3
For each compound, R ¹ corresponds to one row of Table A, R ² is n-propyl and R ³ is methyl. 1 compound.

Table 4
For each compound, R ¹ corresponds to one row of Table A, R ² is n-butyl and R ³ is methyl. 1 compound.

Table 5
For each compound, R ¹ corresponds to one row of Table A, R ² is n-propyl and R ³ is methyl. 2 compounds.

Table 6
For each compound, R ¹ corresponds to one row of Table A, R ² is n-butyl and R ³ is methyl. 2 compounds.

  Compound I is suitable as a fungicide. These are a broad range of plants from the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes classes, especially from the Oomycetes class Distinguish by distinctive effects on sexual pathogenic fungi. Some act osmotically and they can be used for plant protection as foliar fungicides, seed dressing fungicides and soil fungicides.

  These include various cultivated plants such as wheat, rye, barley, oats, rice, corn, grass, banana, cotton, soybeans, coffee, sugarcane, grapes, fruits and houseplants, cucumbers, beans, tomatoes, potatoes and cucumbers etc. This is particularly important in the control of many vegetables and many fungi on the seeds of these plants.

They are particularly suitable for controlling the following plant diseases:
・ Alternaria species for vegetables, rapeseed, sugar beet, fruits and rice (eg A. solani or A. alternata for potatoes and other plants),
・ Aphanomyces species on sugar beet and vegetables,
Bipolaris and Drechslera species on corn, cereals, rice, and grass (eg D. teres wheat on barley) tritci-repentis)),
・ Blumeria graminis (powder disease) on cereals,
Botrytis cinerea (gray mold) on strawberries, vegetables, flowers, and grapes
・ Bremia lactucae on lettuce,
・ Cerospora species (e.g. C. beticula for sugar beet), corn, soybean, rice and sugar beet,
• Cochliobolus species on corn, cereals and rice (eg, Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice),
・ Colletotricum species (eg C. acutatum on various plants), which are found on soybeans, cotton and other plants,
・ Exserohilum seeds on corn,
・ Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbitaceae plants,
-Fusarium and Verticillium species (eg V. dahliae and F. graminearum on wheat) on various plants,
・ Gaeumanomyces graminis on cereals,
・ Gibberella species (such as Gibberella fujikuroi) that are attached to cereals and rice,
・ Grain staining complex for rice,
・ Helminthosporium species (e.g., H. graminicola) on corn and rice,
・ Michrodochium nivale on cereals,
• Mycosphaerella species (eg, H. graminicola on wheat, M. fijiesis on banana) on cereals, bananas and groundnuts,
・ Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans,
・ Phomopsis species on soybeans, sunflowers and grapes (eg P. viticola on grapes, P. helianthii on sunflowers),
・ Phytophthora infestans on potatoes and tomatoes,
・ Plasmopara viticola with grapes,
・ Podosphaera leucotricha on apples,
・ Pseudocercosporella herpotrichoides (Pseudocercosporella herpotrichoides),
・ Pseudoperonospora species (such as P. cubenis) that attach to hops and cucumbers,
• Puccinia species on cereals, maize and asparagus (eg P. triticina and P. striformis on wheat, P. asparagi on asparagus ( P. asparagi)),
・ Pyrenophora species on cereals,
・ Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.attenuatum, Entyloma oryzae,
・ Pyricularia grisea on grass and cereals,
・ Pythium seeds on grass, rice, corn, cotton, rapeseed, sunflower, sugar beet, vegetables and other plants,
-Rhizoctonia species (eg, S. solani) that attach to cotton, rice, potato, lawn, corn, rapeseed, sugar beet, vegetables and other plants,
・ Sclerotinia species (eg, S. sclerotiorum), which are attached to rapeseed, sunflower and other plants,
-Septoria tritici and Stagonospora nodorum on wheat,
・ Erysiphe (syn. Uncinula necator) attached to grape,
・ Setospaeria seeds on corn and grass
・ Sphacelotheca reilinia on corn,
・ Thievaliopsis species on soybean and cotton,
・ Tilletia seeds on cereals,
• Ustilago species on cereals, corn and sugar beet, and • Venturia species (scabies) on apples and pears (eg, V. inaequalis on apples).

  They control harmful fungi from the class of Oomycetes such as Peronospora, Phytophthora, Plasmopara viticola and Pseudoperonospora Especially suitable for.

  Moreover, Compound I is suitable for controlling harmful fungi in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and the protection of stored products. In the protection of wood, particular attention is paid to the following harmful fungi: Ophiostoma species, Ceratocystis species, Aureobasidium pullulans, Sclerophoma species, Chaetomium species, Humicola species, Petriella species and Trichurus species such as Ascomycetes; Coniophora species, Coriolus species, Gloeophyllum species, Lentinus Basidiomycetes such as (Lentinus) species, Pleurotus species, Poria species, Serpula species and Tyromyces species; Aspargillus species, Cladosporium species, Penicillium (Penicillium) species, Trichoderma species, Alternaria ( Incomplete fungi such as Alternaria species, Paecilomyces species; Zygomycetes, such as Mucor species; and in the protection of materials, the following yeasts: Candida species and Saccharomyces cerevisae ).

  Compound I is used to treat fungi or plants, seeds, materials or soils to be protected from fungal attack with a bactericidal amount of active compound. It can be used both before or after the material, plant or seed is infected with the fungus.

  In general, the bactericidal composition comprises 0.1 to 95% by weight of active compound, preferably 0.5 to 90%.

  When used for plant protection, the amount used depends on the type of effect desired and is 0.01 to 2.0 kg of active compound per hectare (ha).

  Seed treatment generally requires an active compound in an amount of 1-1000 g, preferably 5-100 g, per 100 kg of seed.

  When used in the protection of materials or stored products, the amount of active compound applied depends on the type of application site and the desired effect. The usual amount applied to protect the material is, for example, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg of active compound per cubic meter of material to be treated.

  The compounds of formula I can exist in various crystal modifications and their biological activity can be different. They also form part of the subject matter of the present invention.

  Compound I can be processed into conventional formulations such as solvents, emulsions, suspensions, microparticles, powder formulations, pastes and granules. The form of use depends on the specific purpose. In any case, a fine and uniform distribution of the compounds according to the invention must be ensured.

  The formulations are prepared in a known manner, for example by dispersing the active compound with solvents and / or carriers, if desired using emulsifiers and dispersants. Suitable solvents / adjuvants are essentially the following:

  Water, aromatic solvents (eg, Solvesso products, xylene), paraffins (eg, mineral oil fraction), alcohols (eg, methanol, butanol, pentanol, benzyl alcohol), ketones (eg, cyclohexanone, gamma-butyrolactone) ), Pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used;

  Supports such as ground natural minerals (eg kaolin, clay, talc, chalk) and ground synthetic minerals (eg highly dispersed silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (eg polyoxy Ethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates), and dispersants such as lignosulfite effluent and methylcellulose.

  Suitable surfactants include lignosulfonic acid, naphthalene sulfonic acid, phenol sulfonic acid, dibutyl naphthalene sulfonic acid, alkyl aryl sulfonate, alkyl sulfate, alkyl sulfonate, fatty alcohol sulfate, fatty acid and sulfated fatty alcohol glycol ethers. Alkali metal salts, alkaline earth metal salts and ammonium salts, as well as condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, Ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenol Polyglycol ether, tristearyl phenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol Ether acetals, sorbitol esters, lignosulfite waste liquors, and methylcellulose.

  Suitable for preparing directly sprayable solutions, emulsions, pastes or oil dispersions are medium to high boiling mineral oil fractions, such as kerosene or diesel oil, as well as coal tar oil and vegetable oil or Animal oils, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone or strong solvents For example, dimethyl sulfoxide, N-methylpyrrolidone and water.

  Powders, materials for spreading and dustable products can be prepared by mixing or pulverizing the active substance with a solid carrier at the same time.

  Granules, such as coated granule, impregnated granule, homogenous granule and the like, can be prepared by binding the active compound to a solid support. Examples of solid carriers are mineral earth (eg silica gel, silicate, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, ocher, clay, dolomite, diatomaceous earth, sulfuric acid Calcium, magnesium sulfate, magnesium oxide and ground synthetic materials), fertilizers (eg ammonium sulfate, ammonium phosphate, ammonium nitrate and urea), plant-derived products (eg cereal flour, bark flour, wood flour, nut shells) Powder and cellulose powder), and another solid carrier.

  In general, the formulations comprise 0.01 to 95% by weight of active compound, preferably 0.1 to 90%. The active compound is used in a purity (from NMR spectrum) of 90-100%, preferably 95-100%.

  Formulation Examples: Formulation for dilution with water

A. Water-soluble concentrates (SL, LS)
10 parts by weight of the active compound are dissolved in 90 parts by weight of water or a water-soluble solvent. Alternatively, a wetting agent or another adjuvant is added. The active compound dissolves when diluted with water. In this way, a formulation having an active compound content of 10% by weight is obtained.

B. Dispersible concentrates (DC)
20 parts by weight of the active compound are dissolved in 70 parts by weight of cyclohexanone by adding 10 parts by weight of a dispersant (eg polyvinylpyrrolidone). Dilute with water to obtain a dispersion. The active compound content is 20% by weight.

C. Emulsifiable concentrates (EC)
15 parts by weight of the active compound are dissolved in 75 parts by weight of xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (both 5 parts by weight). Dilute with water to obtain an emulsion. The active compound content of the formulation is 15% by weight.

D. Emulsions (EW, EO, ES)
25 parts by weight of the active compound are dissolved in 35 parts by weight of xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (both 5 parts by weight). This mixture is added to 30 parts by weight of water using an emulsifier (eg Ultraturax) to make a homogeneous emulsion. Dilute with water to obtain an emulsion. The active compound content of the formulation is 25% by weight.

E. Suspensions (SC, OD, FS)
In a stirred ball mill, 20 parts by weight of the active compound are subdivided by adding 10 parts by weight of a dispersant and wetting agent and 70 parts by weight of water or an organic solvent to obtain a fine active compound suspension. Dilution with water gives a stable suspension of the active compound. The active compound content of the formulation is 20% by weight.

F. Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of active compound are pulverized with addition of 50 parts by weight of dispersant and wetting agent and hydrated granules using special equipment (eg extruders, spray towers, fluidized beds, etc.) Or as a water-soluble granule. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 50% by weight.

G. Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
75 parts by weight of active compound are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersant and wetting agent and silica gel. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight.

H. Gel formulations
In a ball mill, 20 parts by weight of active compound, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or organic solvent are ground to obtain a fine suspension. Dilution with water gives a stable suspension with 20% by weight of active compound.

  2. Products applied without dilution

I. Dustable powder (DP, DS)
5 parts by weight of active compound are pulverized and mixed thoroughly with 95 parts by weight of finely divided kaolin. This gives a dispersible preparation with an active compound content of 5% by weight.

J. et al. Granules (GR, FG, GG, MG)
0.5 parts by weight of active compound are finely ground and combined with 99.5 parts by weight of carrier. Current methods are extrusion, spray drying or fluidized bed. This gives granules to be applied undiluted with an active compound content of 0.5% by weight.

K. ULV solution (UL)
10 parts by weight of the active compound are dissolved in 90 parts by weight of an organic solvent (eg xylene). This gives a product to be applied undiluted with an active compound content of 10% by weight.

  For seed treatment, generally water soluble agents (LS), suspension formulations (FS), dusting powders (DS), wettable powders and aqueous solvents (WS, SS), emulsion formulations (ES), emulsions ( EC) as well as gel preparations (GF) are used. These formulations can be applied to the seed undiluted or preferably diluted. Can be applied before sowing.

  The active compounds can be used in their formulation or use forms prepared from the formulation, for example directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusting powders, spraying substances or As the form of granules, it can be used by spraying, spraying, dusting, spreading or pouring. The use form depends solely on its intended purpose; in any case, such use forms must ensure the finest possible dispersion of the active compounds according to the invention.

  Aqueous use forms can be prepared from emulsions, pastes or wettable powders (spraying powders, oil dispersions) by adding water. To prepare an emulsion, paste, or oil dispersion, the material (as is or dissolved in an oil or solvent) is homogenized in water using a wetting agent, tackifier, dispersant, or emulsifier. be able to. Alternatively, concentrates can be prepared that contain the active substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, a solvent or oil, suitable for dilution with water.

  The concentration of the active compound in the ready-to-use preparation can be varied within a relatively wide range. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.

  The active compound can also be used successfully in the ultra-low volume (ULV) method, whereby applying formulations containing more than 95% by weight of active compound or adding additives It is even possible to apply the active compound instead.

  Various types of oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides and bactericides can be added to the active compounds, if appropriate, even immediately before use (tank mixing). These agents can be mixed with the agents of the present invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

  Suitable adjuvants in this sense are in particular: organically modified polysiloxanes (eg Break Thru S240®); alcohol alkoxylates (eg Atplus 245®, Atplus MBA1303®, Plurafac LF300® and Lutensol ON30®); EO / PO block polymers (eg Pluronic RPE2035® and Genapol B®); alcohol ethoxylates (eg Lutensol XP80®) ) And sodium dioctyl sulfosuccinate (eg Leophen RA®).

  The formulations of the present invention may coexist with other active compounds such as herbicides, insecticides, growth regulators, fungicides, or fertilizers in their use as fungicides. Mixing compound I or a composition containing it with one or more other active compounds, especially fungicides, can in many cases broaden the activity spectrum or suppress the development of resistance. In many cases, a synergistic effect is obtained.

  The following list of fungicides that can be used with the compounds of the present invention is illustrative of possible combinations and is not limiting:

Strobilurins <br/> azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim - methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, methyl (2-Chloro-5- [1- (3-methylbenzyloxyimino) ethyl] benzyl) carbamate, methyl (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl ) Carbamate, methyl 2- (ortho-((2,5-dimethylphenyloxymethylene) phenyl) -3-methoxyacrylate;

Carboxamides <br/> carboxymethyl anilide type: benalaxyl, Benodaniru, boscalid, carboxin, mepronil, Fenfuramu, fenhexamid, flutolanil, furametpyr, metalaxyl, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, N -(4'-bromobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide, N- (4'-trifluoromethylbiphenyl-2-yl) -4-difluoromethyl-2 -Methylthiazole-5-carboxamide, N- (4'-chloro-3'-fluorobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide, N- (3 ', 4 '-Dichloro-4-fluorobiphenyl-2-yl) -3-difluoromethyl-1-methylpyrazole-4-carboxamide, N- (2-cyanophenyl) -3,4-dichloro Loisothiazole-5-carboxamide;
Carboxylic acid morpholides: dimethomorph, fullmorph;
Benzamides: flumetovar, fluopicolide (picobenzamide), zoxamide;
Other carboxamides: carpropamide, diclocimet, mandipropamide, N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-methanesulfonylamino-3- Methylbutyramide, N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-ethanesulfonylamino-3-methylbutyramide;

Azoles Triazoles: vitertanol, bromoconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriazole, hexaconazole, imibenco Nazole, ipconazole, metconazole, microbutanyl, penconazole, propiconazole, prothioconazole, cimeconazole, tebuconazole, tetraconazole, triadimenol, triadimethone, triticonazole;
Imidazoles: cyazofamide, imazalyl, pefazoate, prochloraz, triflumizole;
Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;
Others: ethaboxam, etridiazole, himexazole;

Nitrogen-containing heterocyclyl compounds Pyridines: fluazinam, pyrifenox, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine;
Pyrimidines: bupyrimeto, cyprodinil, ferrimzone, fenarimol, mepanipyrim, nuarimol, pyrimethanil;
Piperazines: triforin;
Pyrroles: fludioxonil, fenpiclonyl;
Morpholines: aldimorph, dodemorph, fenpropimorph, tridemorph;
Dicarboximides: iprodione, procymidone, vinclozolin;
Other: acibenzoral-S-methyl, anilazine, captan, captahol, dazomet, diclomedin, phenoxanyl, holpet, fenpropidin, famoxadone, fenamidone, octirinone, probenazole, proquinazide, pyroxylone, quinoxyphene, tricyclazole, 5-chloro-7- ( 4-Methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl)-[1,2,4] triazolo [1,5-a] pyrimidine, 2-butoxy-6-iodo-3 -Propylchromen-4-one, N, N-dimethyl-3- (3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4] triazole-1-sulfonamide;

Carbamates and dithiocarbamates Dithiocarbamates : felbam, mancozeb, manneb, methylam, metam, propineb, tillam, dineb, ziram;
Carbamates: dietofencarb, fullbenchavalicarb, iprovaricarb, propamocarb, methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propionate, 4-fluorophenyl N- ( 1- (1- (4-cyanophenyl) ethanesulfonyl) but-2-yl) carbamate;

Other fungicides : Guanidines: dodin, iminoctadine, guazatine;
Antibiotics: kasugamycin, polyoxin, streptomycin, validamycin A;
Organometallic compound: fentin salt;
Sulfur-containing heterocyclyl compounds: isoprothiolane, dithianon;
Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenphos, pyrazophos, tolcrophos-methyl, phosphorous acid and its salts;
Organochlorine compounds: thiophanate methyl, chlorothalonil, diclofluuride, tolyl fluanide, fursulfamide, phthalide, hexachlorobenzene, pencyclon, quintozen;
Nitrophenyl derivatives: binapacryl, dinocup, dinobutone;
Inorganic active compounds: Bordeaux solution, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
Others: Spiroxamine, cyflufenamide, simoxanyl, metraphenone.

Example of action against harmful fungi The bactericidal action of the compounds of formula I was demonstrated by the following tests:
The active compound is used in a 99: 1 solvent: emulsifier volume ratio of acetone and / or DMSO and an emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols). A stock solution containing 25 g of active compound was made up to 10 ml. The mixture was then made up to 100 ml with water. The stock solution was diluted to the active compound concentration described below using the solvent / emulsifier / water mixture described.

Synthetic Examples The methods described in the following synthetic examples are used to prepare other compounds I by appropriate modification of the starting compounds. The resulting compounds are listed in the table below with physical data.

Example 1: Preparation of 2-pentanolyloctanenitrile
At 30 ° C., a solution containing 17.92 g (160 mmol) potassium tert-butoxide in 50 ml dimethylformamide (DMF) was added dropwise into a solution containing 10.0 g (80 mmol) octanenitrile in 50 ml DMF. Then 10.40 g (30 mmol) of ethyl valerate was added dropwise and the mixture was stirred at 20-25 ° C. overnight. The solvent was distilled off under reduced pressure, the residue was dissolved in water and extracted with cyclohexane. The organic layer was discarded and the aqueous layer was acidified with concentrated HCl and extracted with methyl tert-butyl ether (MTBE). The combined organic extracts were washed with water and then dehydrated. The solvent was removed to give 10.59 g of the title compound as a brown oil, which was used further directly.

Example 2: Preparation of 5-butyl-6-hexyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine
10 ml of mesitylene contain 1.20 g (5.7 mmol) of ketonitrile from Example 1, 0.55 g (5.7 mmol) of 5-methylpyrazol-3-amine and 0.21 g (1.1 mmol) of p-toluenesulfonic acid. The solution was heated at 180 ° C. for 3 hours. The solvent was then removed in vacuo and the residue was taken up in dichloromethane and washed with water and NaHCO ₃ solution. The organic layer was dehydrated, the solvent was removed in vacuo, and the residue was triturated with pentane. The residue was the title compound as light brown crystals with a melting point of 1.32 g of 134-136 ° C.

Example of use Protective activity against Puccinia recondita in wheat (red rust of wheat)
An aqueous suspension having the active compound concentration described below was sprayed onto the leaves of potted wheat seedlings of the cultivar “Kanzler” until the liquid dripped. The next day, the treated plants were inoculated with a spore suspension of wheat rust (Puccinia recondita). The plants were then placed in a room with high atmospheric humidity (90-95%) at 20-22 ° C. for 24 hours. During this time, the spores germinated and the germ tube penetrated into the leaf tissue. The next day, the test plants were returned to the greenhouse and cultivated for an additional 7 days at a temperature of 20-22 ° C. and a relative atmospheric humidity of 65-70%. Next, the degree of leaf rust generation was determined visually.

  In this test, plants treated with 250 ppm of active compound I-2, I-3 or I-4 were infected up to 1%, whereas untreated plants were 90% infected.

The following results were obtained by comparison with the closest prior art.

Claims (12)

Formula I:

[Wherein the substituents are as defined below:
R ¹ is C ₅ -C ₉ -alkyl, C ₄ -C ₁₁ -alkoxymethylene or C ₃ -C ₁₀ -alkoxyethylene, wherein the aliphatic group may be substituted by 1 to 3 of the following groups: Often:
Cyano, nitro, hydroxy, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkylthio, C ₅ -C ₁₂ -alkynyl and NR ^a R ^b ;
R ^a and R ^b are hydrogen or C ₁ -C ₆ -alkyl;
R ² is n-propyl or n-butyl;
A is N or CH;
R ³ is CH ₃ , and further hydrogen when A is CH]
Azoropyrimidine.   2. A compound of formula I according to claim 1, wherein A is CH. R ¹ has nine carbon atoms up to, or an unsubstituted straight-chain, or a single branch, alkyl chains of a double branched or triple branch, a compound of formula I according to claim 1 or 2. R ² is n- propyl, compounds of formula I according to any one of claims 1 to 3. R ² is n- butyl, compound of formula I according to any one of claims 1 to 3. The following compounds:
6-hexyl-2-methyl-5-propylpyrazolo [1,5-a] pyrimidin-7-ylamine;
6-heptyl-2-methyl-5-propylpyrazolo [1,5-a] pyrimidin-7-ylamine;
2-methyl-6-octyl-5-propylpyrazolo [1,5-a] pyrimidin-7-ylamine;
2-methyl-6-nonyl-5-propylpyrazolo [1,5-a] pyrimidin-7-ylamine;
5-butyl-6-hexyl-2-methylpyrazolo [1,5-a] pyrimidin-7-ylamine;
5-butyl-6-heptyl-2-methylpyrazolo [1,5-a] pyrimidin-7-ylamine;
5-butyl-2-methyl-6-octylpyrazolo [1,5-a] pyrimidin-7-ylamine;
5-butyl-2-methyl-6-nonylpyrazolo [1,5-a] pyrimidin-7-ylamine;
The compound of formula I according to claim 1, wherein 6. A process for the preparation of a compound of formula I according to any one of claims 1-5, comprising a compound of formula II:

[Wherein R is C ₁ -C ₄ -alkyl]
The β-ketoester of formula III:

Of the formula IV:

Of 7-hydroxyazolopyrimidine, which is halogenated to give the formula V:

[Wherein Hal is chlorine or bromine]
The above process wherein the compound is obtained and V is reacted with ammonia. A process for the preparation of a compound of formula I according to any one of claims 1-6, comprising a compound of formula VI:

A process as claimed in claim 7 wherein the acyl cyanide of formula III is reacted with an aminoazole of formula III according to claim 7.   A composition comprising a solid or liquid carrier and a compound of formula I according to any one of claims 1-6.   The composition of claim 9 further comprising an active compound.   Seeds comprising a compound of formula I according to any one of claims 1 to 6 in an amount of 1 to 1000 g per 100 kg.   A method for controlling phytopathogenic harmful fungi, wherein the fungus or a material, plant, soil or seed to be protected against fungal attack is in an effective amount. A process as described above, which is treated with a compound of formula I as described in paragraph 2.